U.S. patent number 8,273,166 [Application Number 13/008,783] was granted by the patent office on 2012-09-25 for phase change ink compositions and colorants for use in the same.
This patent grant is currently assigned to Xerox Corporation. Invention is credited to Biby E. Abraham, C. Geoffrey Allen, Maria Birau, Peter G. Odell, Caroline M. Turek.
United States Patent |
8,273,166 |
Birau , et al. |
September 25, 2012 |
**Please see images for:
( Certificate of Correction ) ** |
Phase change ink compositions and colorants for use in the same
Abstract
A phase change ink compositions, comprising a novel colorant wax
to prevent and/or reduce printhead and nozzle contamination in ink
jet printers caused by drooling and faceplate staining. In
particular, there is provided novel colorants containing acid
groups for use in phase change ink compositions and which are
compatible with phase change ink components.
Inventors: |
Birau; Maria (Mississauga,
CA), Allen; C. Geoffrey (Waterdown, CA),
Abraham; Biby E. (Mississauga, CA), Turek; Caroline
M. (Mississauga, CA), Odell; Peter G.
(Mississauga, CA) |
Assignee: |
Xerox Corporation (Norwalk,
CT)
|
Family
ID: |
46489772 |
Appl.
No.: |
13/008,783 |
Filed: |
January 18, 2011 |
Prior Publication Data
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|
|
|
Document
Identifier |
Publication Date |
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US 20120180694 A1 |
Jul 19, 2012 |
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Current U.S.
Class: |
106/31.29;
106/31.47; 106/31.92; 106/31.64; 106/31.32; 106/31.61 |
Current CPC
Class: |
C09D
11/32 (20130101); C09D 11/34 (20130101) |
Current International
Class: |
C09D
11/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Surfactant science and technology, ACS National Meeting, New
Orleans, Apr. 9-10, 2008. cited by examiner .
SciFinder Abstract for US 2003/0149134. cited by examiner.
|
Primary Examiner: Mayes; Melvin C
Assistant Examiner: Qian; Yun
Attorney, Agent or Firm: Pillsbury Winthrop Shaw Pittman
LLP
Claims
What is claimed is:
1. A phase change ink composition comprising: a colorant; and a wax
ink vehicle, wherein the colorant further comprises a compound
selected from the group consisting of ##STR00003## and the colorant
is insoluble in water and polar organic solvents but is soluble in
the wax ink vehicle.
2. The phase change ink composition of claim 1 having a drool
pressure in a printer of at least 1.5 inches water.
3. The phase change ink composition of claim 2 having a drool
pressure in a printer of from about 1.5 inches of water to about
4.0 inches of water.
4. The phase change ink composition of claim 3 having a drool
pressure in a printer of from about 2.8 inches of water to about
4.0 inches of water.
5. The phase change ink composition of claim 1 exhibiting little to
no staining through visual observation.
6. The phase change ink composition of claim 1, wherein the
colorant is present in the phase change ink composition in an
amount of from about 0.1 to about 50 percent by weight of the total
weight of the phase change ink composition.
7. The phase change ink composition of claim 6, wherein the
colorant is present in the phase change ink composition in an
amount of from about 0.2 to about 20 percent by weight of the total
weight of the phase change ink composition.
8. The phase change ink composition of claim 7, wherein the
colorant is present in the phase change ink composition in an
amount of from about 0.5 to about 10 percent by weight of the total
weight of the phase change ink composition.
9. The phase change ink composition of claim 1 further comprising a
dispersant selected from the group consisting of
polyethyleneimines, polymers containing quaternary ammonium salts,
polymers containing polyalkylated succinimides, and mixtures
thereof.
10. The phase change ink composition of claim 1, wherein the
dispersant is present in the phase change ink composition in an
amount of from about 0.1 to about 25 percent by weight of the total
weight of the phase change ink composition.
11. The phase change ink composition of claim 10, wherein the
dispersant is present in the phase change ink composition in an
amount of from about 0.5 to about 10 percent by weight of the total
weight of the phase change ink composition.
12. The phase change ink composition of claim 11, wherein the
dispersant is present in the phase change ink composition in an
amount of from about 1 to about 6 percent by weight of the total
weight of the phase change ink composition.
13. The phase change ink composition of claim 1 exhibiting less
.DELTA.(Drool Pressure) than that of a phase change ink composition
without the colorant.
14. The phase change ink composition of claim 1 exhibiting no
banding.
15. The phase change ink composition of claim 1 exhibiting uniform
optical density when printed wherein the coefficient of variation
of measured optical densities is less than about 6%.
16. A phase change ink composition comprising: a colorant; and an
ink vehicle, wherein the colorant further comprises a compound
selected from the group consisting of ##STR00004##
17. A phase change ink composition comprising: a colorant; a
dispersant; and a wax ink vehicle, wherein the colorant further
comprises a compound selected from the group consisting of
##STR00005## further wherein the colorant is insoluble in water and
polar organic solvents but is soluble in the wax ink vehicle.
Description
BACKGROUND
The present embodiments relate generally to phase change ink
compositions, and in particular, acid colorants for use in phase
change ink compositions to prevent and/or reduce printhead and
nozzle contamination in ink jet printers caused by drooling and
faceplate staining. Phase change ink or solid ink compositions are
characterized by being solid at room temperature and molten at an
elevated temperature at which the molten ink is applied to a
substrate. These phase change ink compositions generally comprise
an ink vehicle and a colorant, and can be used for ink jet
printing.
Phase change ink or solid ink printers conventionally receive ink
in a solid form, which is sometimes referred to as ink sticks. The
ink sticks are typically inserted through an insertion opening of
an ink loader for the printer and are moved by a feed mechanism
and/or gravity toward a heater plate. The heater plate melts the
phase change ink impinging on the plate into a liquid that is
delivered to a printhead assembly for jetting onto a recording
medium. The recording medium is typically paper or a liquid layer
supported by an intermediate imaging member, such as a metal drum
or belt.
A printhead assembly of a phase change ink printer typically
includes one or more printheads each having a plurality of ink jets
from which drops of melted phase change ink are ejected towards the
recording medium. The ink jets of a printhead receive the melted
ink from an ink supply chamber, or manifold, in the printhead
which, in turn, receives ink from a source, such as a melted ink
reservoir or an ink cartridge. Each ink jet includes a channel
having one end connected to the ink supply manifold. The other end
of the ink channel has an orifice, or nozzle, for ejecting drops of
ink. The nozzles of the ink jets may be formed in an aperture, or
nozzle plate that has openings corresponding to the nozzles of the
ink jets. During operation, drop ejecting signals activate
actuators in the ink jets to expel drops of fluid from the ink jet
nozzles onto the recording medium. By selectively activating the
actuators of the ink jets to eject drops as the recording medium
and/or printhead assembly are moved relative to each other, the
deposited drops can be precisely patterned to form particular text
and graphic images on the recording medium.
One difficulty faced by fluid ink jet systems is that organic
pigments and dyes used in the phase change inks show drooling
behavior and faceplate staining in the printhead. Drooling is
defined as the burst of the ink out of the printhead when pressure
is applied and is expressed in differential inches water in the Low
Pressure Assist cycle (LPA). Staining represents the fouling of the
faceplate by the ink.
Experimental trials indicated that one approach for solving drool
and staining of the faceplate by phase change inks may be through
the use of colorants containing acid groups. It has been found that
drooling and staining is strongly correlated to performance of the
inks. However, commercially available colorants cannot be used
since they exhibit a strong gelling behavior in phase change ink.
Therefore, the present embodiments provide an acid colorant that
can be used in phase change inks and which addresses the problems
described above.
SUMMARY
According to embodiments illustrated herein, there is provided
novel acid colorant for use in phase change ink compositions.
In particular, the present embodiments provide a phase change ink
composition comprising: a colorant; and a wax ink vehicle, wherein
the colorant is a compound having one or more functional acid
groups and a N-alkyl or N-aryl counterion that is quaternary
ammonium NH.sub.4 or an alkyl or aryl quaternary ammonium selected
from the group consisting of tetrabuthylammonium,
teraoctylammonium, teradodecylammonium, tetraoctadecylammonium,
N,N-dimethyl dioctadecyl, N,N-dimethyl dioctyl, N,N-dimethyl
didecyl, and mixtures thereof, wherein the colorant is insoluble in
water and polar organic solvents but is soluble in the wax ink
vehicle.
In further embodiments, there is provided a phase change ink
composition comprising: a colorant; and an ink vehicle, wherein the
colorant further comprises a compound selected from the group
consisting of
##STR00001##
In yet other embodiments, there is provided a phase change ink
composition comprising: a colorant; a dispersant; and a wax ink
vehicle, wherein the colorant further comprises a compound having
one or more functional acid groups and a N-alkyl or N-aryl
counterion that is quaternary ammonium NH.sub.4 or an alkyl or aryl
quaternary ammonium selected from the group consisting of
tetrabuthylammonium, teraoctylammonium, teradodecylammonium,
tetraoctadecylammonium, N,N-dimethyl dioctadecyl, N,N-dimethyl
dioctyl, N,N-dimethyl didecyl, and mixtures thereof, and further
wherein the colorant is insoluble in water and polar organic
solvents but is soluble in the wax ink vehicle.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present embodiments, reference
may be had to the accompanying figures.
FIG. 1 illustrates an example of a domesticated acid dyes according
to the present embodiments;
FIG. 2 illustrates another example of a domesticated acid dyes
according to the present embodiments;
FIG. 3A demonstrates a banding test page at the initial state of a
jettable phase change ink immediately after being loaded into the
printer according to the present embodiments;
FIG. 3B demonstrates a banding test page after 3 days in a printer
for the phase change ink of FIG. 3A;
FIG. 4A demonstrates a banding test page at Day 0 for another phase
change ink according to the present embodiments;
FIG. 4B demonstrates a banding test page at Day 3 for the phase
change ink of FIG. 4A;
FIG. 5A demonstrates a banding test page at Day 0 for a comparative
phase change ink; and
FIG. 5B demonstrates a banding test page at Hour 17 for the phase
change ink of FIG. 5A.
DETAILED DESCRIPTION
In the following description, it is understood that other
embodiments may be utilized and structural and operational changes
may be made without departure from the scope of the present
embodiments disclosed herein, phase change ink technology broadens
printing capability and customer base across many markets, and the
diversity of printing applications will be facilitated by effective
integration of printhead technology, print process and ink
materials. The phase change ink compositions are characterized by
being solid at room temperature and molten at an elevated
temperature at which the molten ink is applied to a substrate.
However, phase change ink systems also experience problems during
performance at other temperatures including at jetting temperature.
For example, organic pigments and dyes used in phase change inks
can exhibit drooling behavior and faceplate staining on the front
face of the printhead. Drooling is defined as the burst of the ink
out of the printhead whether pressure is applied or not. For
purposes of quantifying drool, it is convenient to express drool of
a given test ink sample against a non-drooling reference such as
the ink base without any colorant and/or dispersant. The
relationship below defines the level of drool for a given test ink.
.DELTA.(Drool Pressure)=Drool Pressure(sample)-Drool
Pressure(reference) It is desirable to have as small as possible a
delta drool pressure of a given ink such that optimum jetting and
print performance can be realized.
Drool pressure of a sample ink is the pressure realized that causes
the ink to burst out of at least some of the nozzles in the
printhead which can be accurately measured by a micropressure
gauge. Drooling of inks in a printhead complicate the jetting
process due to undesirable inter-nozzle color mixing as well as
resulting in the undesirable depletion of ink from the ink loader.
Drool pressure of a reference ink is that pressure realized that
causes the reference ink to burst out of at least some of the
nozzles in the printhead which can be measured by a micropressure
gauge. Typically this pressure value satisfies the requirements for
successful jetting over the many purge and wipe cleaning cycles
that occurs over the lifetime of the printer. Staining of the
printhead is the undesirable fouling of the faceplate by an ink, or
at least a portion of an ink, which can be qualitatively assessed
through visual observation. For example, staining can be seen as
ink smeared on the surface of the faceplate. Thus a desirable
observation is when little or no ink is observed on the faceplate.
A printhead that has been very undesirably compromised by staining
from an ink, or a portion of an ink, will likely be more prone to
ink drooling at even lower applied pressures during the course of
the printer's normal purge and wipe cleaning cycles. In the present
embodiments, there is provided a phase change ink composition that
has a drool pressure in a printer of at least 1.5 inches water. In
further embodiments, the composition has a drool pressure in of
from about 1.5 inches of water to about 4.0 inches of water or of
from about 2.8 inches of water to about 4.0 inches of water.
Most phase change inks containing pigments have problems with
drooling and staining onto the faceplate. One exception are inks
containing Pigment Red 176 which exhibited minimal or controllable
drool behavior at differential pressures, compared to a
commercially available base as a control, from about 0 to about
-0.9 inches of water. In contrast, inks with Hostaperm Blue B4G and
SOLSPERSE 5000 as a synergist exhibited a .DELTA.LPA of -2.4 inches
of water, and inks containing Lyonogen Magenta (Pigment Red 122,
with and without synergist) exhibited a .DELTA.LPA of -1.7 inches
of water.
Banding of a printed member from an ink is defined as the
undesirable non-uniformity of optical density across the page, for
example, across a solid fill print. This is typically caused by
varying proportions of colorant in an ink, typically pigment
particles, that partially settle in the various manifolds of the
jetstack over time thus only allowing the remaining clear base
and/or ink with less than full color strength to be jetted.
Conversely, for the manifolds connected to the nozzles in the
opposite configuration, an enrichment of color can result where
even nozzle clogging can occur. The level of banding and pattern
can depend on the configuration of a given printhead's fluidic
channel system. The level or degree of banding can be both
qualitatively and quantitatively assessed. The level or degree of
banding can be assessed, for example, from the first print out from
an ink that has been aging in a printer for a period of time, for
example, a day or a week. The level or degree of banding can also
be assessed for a series of consecutively formed prints, such as
the first 5 or 10 prints, for example, made from an ink that has
been aging in a printer for a period of time, for example, a day or
a week. The differences in the printed images' optical densities of
consecutive prints made from an ink that has been aging in a
printer for a period of time can indicate the nature of the
micro-settling of the colorant's particles. Inks that are assessed
for banding can be printed on any suitable substrate such as coated
papers, uncoated papers, transparencies and the like.
A qualitative banding assessment of a print typically is
represented by a visual rating system that attempts to define the
presence or absence of discreet banding occurrences, it is
convenient to use a scale that has 5 or 6 banding rating intervals
or up to about 10 banding rating intervals, for example. While a
qualitative visual rating system can be both a powerful and useful
tool in ranking the banding level of a given print, a quantitative
measure of banding allows for a more accurate determination of
banding of a print. Also, image analysis tools can be applied to
assess scanned prints that can yield accurate information on the
jet to jet performance both along and across the print process
path.
Quantitative banding assessment can be measured by various
colorimeters that directly measure X,Y,Z tristimulus values,
densitometers and more desirably by spectrophotometers and
spectrodensitometers. Illuminant types can include type A
(incandescent), type C (sunlight), type D50 (daylight, red shade),
type E (normalized 5500K reference), type D65 (daylight, neutral),
type D75 (daylight, blue shade), type F2 (cool white fluorescent),
type F7 (broad band white fluorescent), Type F11 (TL84 fluorescent)
and type F12 (Ultralume 3000 fluorescent). Suitable optical density
responses include ANSI Status T, DIN Status E and ANSI Status A.
Useful colorimetric outputs of these devices include, but are not
limited to, CIE XYZ, CIE LAB, CIE LUV and CIE LCH conventions.
The presence of banding of an image on a print can be detected by
measuring optical density normal to the print process direction for
at least one location on the print. It is useful to assess banding
from prints having a 100% density solid fill target which serves to
minimize the measured contributions of visible paper from lower
fill densities and thus result in a more accurate measure of the
degree of banding. It is convenient to express the uniformity of
density across the page (that is the direction that is normal to
the print process direction) as a percentage deviation from the
mean optical density where it is desirable for a given print to
have as low a percentage deviation from the mean optical density as
possible. The coefficient of variation of measured optical
densities of a print, herein denoted as banding CV, is defined as
the measured optical densities' standard deviation divided by the
mean optical density multiplied by 100% where it is also desirable
for a given print to have as low a banding CV as possible.
It is desirable for a print to have a banding CV no higher than
about 6%, such as no higher than about 4% and such as no higher
than about 2%.
A synergist or a pigment stabilizer is a compound that promotes the
adsorption of the polymeric dispersant onto the pigment. For
example, in the case of a cationic dispersant, the dispersant
anchor is comprised of a positive charge and will interact with an
anionic group present on the synergist, exchanging counter ions and
promote an anchoring of the dispersant onto the modified pigment
surface. For example, in embodiments, synergists having sulfonic
groups, such as that are in Solsperse 22000, are absorbed onto the
pigment. The sulfonic end groups of the synergist and the
quaternary ammonium end groups of the dispersants interact,
exchanging counter ions and promoting an anchoring of the
dispersant onto the modified pigment surface.
The present embodiments address drooling and faceplate staining by
using a specific type of colorant in the phase change inks.
Commercially available colorants cannot, however, be used because
such colorants exhibit a strong gelling behavior in phase change
ink. For example, inks prepared with commercially available active
polymeric synergist agents SOLSPERSE 5000 (a derivatized sulfonated
copper phthalocyanine) and SOLSPERSE 22000 (a derivatized
sulfonated Pigment Yellow 12) at nominal ink loadings below 1% by
weight (with no pigment added for the purposes of exploring the
concept of the synergist itself being a colorant) exhibited no
drooling or staining behavior. However, when the synergist loading
was increased to or above 2.5% wt (with no pigment added for the
purposes of exploring the concept of the synergist itself being a
colorant) the inks displayed strong gelling behavior. Since
commercially available synergists cannot be used as colorants, the
present embodiments are directed to compounds containing acid
functional groups that can be domesticated as phase change ink
colorants.
As such, the present embodiments provide an acid colorant that can
be used in phase change inks and which addresses the problems
described above. An acid colorant is a compound that contains
functional acid groups and is soluble in water. The colorant must
be modified by replacing the metal counterion with a more suitable
N-alky/aryl counterion which will facilitate compatibility with
phase change ink. Phase change inks prepared with the acid
colorants of the present embodiments were tested for drooling,
staining and banding in a Typhoon printer. All tested inks
demonstrated non-drooling and non-staining behavior and passed a
72-hour banding test at 118.degree. C. As such, the acid colorant
of the present embodiments offers major advantages over previously
used colorants by preventing or reducing undesirable drooling and
staining behavior, thus improving stability of the ink in the
printhead, and also allows for the opportunity to use cheaper
commercial dyes that could be modified for improved performance in
a phase change ink jet printhead.
Acid dyes are compounds in which the coloring component is in the
anion, and such dyes are usually sold as sodium salts of the
corresponding acid functionality (COO.sup.- or SO.sub.3.sup.-).
Because these off the shelf colorants exhibit a strong gelling
behavior in phase change ink, the colorants must be modified by
replacing the metal counterion with a more suitable N-alkyl/aryl
counterion which will allow much improved compatibility with phase
change ink components. Suitable N-alkyl/aryl counterions to be used
in the modification may be selected from the group consisting of
quaternary ammonium NH.sub.4, or any alkyl or aryl quaternary
ammonium, such as tetrabuthylammonium, teraoctylammonium,
teradodecylammonium, tetraoctadecylammonium, N,N-dimethyl
dioctadecyl, N,N-dimethyl dioctyl, N,N-dimethyl didecyl, quaternary
ammonium compounds known as the Arquads, and mixtures thereof.
The quaternary ammonium compounds known as the Arquads are
primarily alkyltrimethylammonium chlorides and may be represented
by the formula R--N(CH.sub.3).sub.3Cl wherein R is a long chain
alkyl group having at least 8 carbon atoms. These particular
quaternary ammonium compounds are marketed by Akzo Nobel N.V. under
the trade-name ARQUAD. A variety of compounds of this class are
available varying as to the length and number of long chain alkyl
groups attached to the nitrogen atom.
FIGS. 1 and 2 present two examples of domesticated acid dyes:
Naphthol Blue-Black and Nitrazine Yellow. The displacement of the
metal by the N-alkyl counterion modifies the solubility parameters
of the compound from being soluble in water and polar organic
solvents to being insoluble in most solvents while being readily
dispersible in the waxy vehicle of phase change ink. Any dye or
pigment that can be modified by replacing the metal counterion with
a more suitable N-alkyl/aryl counterion to allow improved
compatibility with phase change ink components may be used as the
acid colorants of the present embodiments. In embodiments, such
dyes and pigments include, but are not limited to, those containing
at least one carboxylic acid or at least one sulfonic acid group,
and mixtures thereof. Dispersants used in the phase change inks
include, but are not limited to, those selected from the group
consisting of MODAFLOW 2100, available from Cytec Surface
Specialties, OLOA 1200, OLOA 11000, OLOA 11001, available from
Chevron Oronite Company LLC, IRKASPERSE 2153, 2155, SOLSPERSE 9000,
16000, 17000, 17940, 18000, 19000, 19240, 20000, 36000, 39000,
41000, 54000, available from Lubrizol Corporation) and mixtures
thereof. Exemplary ink compositions may include one or more
dispersants and/or one or more surfactants for their known
properties, such as controlling wetting properties of the ink
composition, and stabilizing pigmented colorants.
The acid colorant may be present in the phase change ink in any
desired or effective amount to obtain the desired color or hue such
as, for example, at least from about 0.1 percent by weight of the
ink to about 50 percent by weight of the ink, at least from about
0.2 percent by weight of the ink to about 20 percent by weight of
the ink, and at least from about 0.5 percent by weight of the ink
to about 10 percent by weight of the ink. The dispersant may be
present in the phase change ink in an amount of from about 0.1 to
about 25 percent by weight of the total weight of the ink. In
further embodiments, the dispersant may be present in the phase
change ink in an amount of from about 0.5 to about 10, or from
about 1 to about 6 percent by weight of the total weight of the
ink.
The ink of the present embodiments may further include conventional
additives to take advantage of the known functionality associated
with such conventional additives. Such additives may include, for
example, at least one isocyanate derived material, antioxidant,
defoamer, slip and leveling agents, clarifier, viscosity modifier,
adhesive, plasticizer and the like.
The ink vehicle or carrier may also include at least one isocyanate
derived material. The isocyanate derived material may be a urethane
resin obtained by reacting two equivalents of an alcohol, such as
hydroabietyl alcohol and one equivalent of an isocyanate or
diisocyanate (isophorone diisocyanate), as disclosed in, for
example, Example 1 of U.S. Pat. No. 5,782,966, the disclosure of
which is totally incorporated herein by reference in its entirety.
The isocyanate derived material may be present in the ink carrier
in an amount of from about 2 to about 99 percent or from about 2 to
about 90 percent or from about 3 to about 80 percent by weight of
the ink carrier. Other suitable isocyanate-derived materials
include a urethane resin that was the adduct of three equivalents
of stearyl isocyanate and a glycerol-based alcohol, prepared as
described in Example 4 of U.S. Pat. No. 6,309,453, the disclosure
of which is totally incorporated herein by reference in its
entirety.
The ink may optionally contain antioxidants to protect the images
from oxidation and also may protect the ink components from
oxidation while existing as a heated melt in the ink reservoir.
Examples of suitable antioxidants include (1) N,N'-hexamethylene
bis(3,5-di-tert-butyl-4-hydroxy hydrocinnamamide) (IRGANOX 1098,
available from Ciba Inc.), (2)
2,2-bis(4-(2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy))
ethoxyphenyl)propane (TOPANOL-205, available from ICI America
Corporation), (3) tris(4-tert-butyl-3-hydroxy-2,6-dimethyl
benzyl)isocyanurate (CYANOX 1790, 41, 322-4, LTDP, Aldrich
D12,840-6), (4) 2,2'-ethylidene bis(4,6-di-tert-butylphenyl)fluoro
phosphonite (ETHANOX-398, available from Ethyl Corporation), (5)
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphonite
(ALDRICH 46,852-5; hardness value 90), (6) pentaerythritol
tetrastearate (TCI America #P0739), (7) tributylammonium
hypophosphite (Aldrich 42,009-3), (8)
2,6-di-tert-butyl-4-methoxyphenol (Aldrich 25,106-2), (9)
2,4-di-tert-butyl-6-(4-methoxybenzyl)phenol (Aldrich 23,008-1),
(10) 4-bromo-2,6-dimethylphenol (Aldrich 34,951-8), (11)
4-bromo-3,5-didimethylphenol (Aldrich B6,420-2), (12)
4-bromo-2-nitrophenol (Aldrich 30,987-7), (13) 4-(diethyl
aminomethyl)-2,5-dimethylphenol (Aldrich 14,668-4), (14)
3-dimethylaminophenol (Aldrich 1014,400-2), (15)
2-amino-4-tert-amylphenol (Aldrich 41,258-9), (16)
2,6-bis(hydroxymethyl)-p-cresol (Aldrich 22,752-8), (17)
2,2'-methylenediphenol (Aldrich B4,680-8), (18)
5-(diethylamino)-2-nitrosophenol (Aldrich 26,951-4), (19)
2,6-dichloro-4-fluorophenol (Aldrich 28,435-1), (20) 2,6-dibromo
fluoro phenol (Aldrich 26,003-7), (21) .alpha.-trifluoro-o-creso-1
(Aldrich 21,979-7), (22) 2-bromo-4-fluorophenol (Aldrich 30,246-5),
(23) 4-fluorophenol (Aldrich F1,320-7), (24)
4-chlorophenyl-2-chloro-1,1,2-tri-fluoroethyl sulfone (Aldrich
13,823-1), (25) 3,4-difluoro phenylacetic acid (Adrich 29,043-2),
(26) 3-fluorophenylacetic acid (Aldrich 24,804-5), (27)
3,5-difluoro phenylacetic acid (Aldrich 29,044-0), (28)
2-fluorophenylacetic acid (Aldrich 20,894-9), (29) 2,5-bis
(trifluoromethyl) benzoic acid (Aldrich 32,527-9), (30)
ethyl-2-(4-(4-(trifluoromethyl)phenoxy)phenoxy)propionate (Aldrich
25,074-0), (31) tetrakis (2,4-di-tert-butyl phenyl)-4,4'-biphenyl
diphosphonite (Aldrich 46,852-5), (32) 4-tert-amyl phenol (Aldrich
15,384-2), (33) 3-(2H-benzotriazol-2-yl)-4-hydroxy phenethylalcohol
(Aldrich 43,071-4), NAUGARD 76, NAUGARD 445, NAUGARD 512, AND
NAUGARD 524 (manufactured by Chemtura Corporation), and the like,
as well as mixtures thereof. The antioxidant, when present, may be
present in the ink in any desired or effective amount, such as from
about 0.25 percent to about 10 percent by weight of the ink or from
about 1 percent to about 5 percent by weight of the ink.
The ink may further contain an optional viscosity modifier such as
FORAL 85, a glycerol ester of hydrogenated abietic (rosin) acid
(commercially available from Eastman), FORAL 105, a pentaerythritol
ester of hydroabietic (rosin) acid (commercially available from
Eastman), CELLOLYN 21, a hydroabietic (rosin) alcohol ester of
phthalic acid (commercially available from Eastman), ARAKAWA KE-311
and KE-100 Resins, triglycerides of hydrogenated abietic (rosin)
acid (commercially available from Arakawa Chemical Industries,
Ltd.), synthetic polyterpene resins such as NEVTAC 2300, NEVTAC
100, and NEVTACO 80 (commercially available from Neville Chemical
Company), WINGTACK 86, a modified synthetic polyterpene resin
(commercially available from Sartomer), and the like. Viscosity
modifiers may be present in the ink in any effective amount, such
as from about 0.01 percent by weight of the ink to from about 98
percent by weight of the ink, from about 0.1 percent by weight of
the ink to about 50 percent by weight of the ink, from about 5
weight percent of the ink to about 10 weight percent of the
ink.
Adhesives, such as VERSAMID 757, 759, or 744 (commercially
available from Cognis) may be present in the ink from about 0.01
percent by weight of the ink to from about 98 percent by weight of
the ink, from about 0.1 percent by weight of the ink to about 50
percent by weight of the ink, from about 5 weight percent of the
ink to about 10 weight percent of the ink.
Plasticizers such as UNIPLEX 250 (commercially available from
Unitex), the phthalate ester plasticizers commercially available
from Ferro under the trade name SANTICIZER, such as dioctyl
phthalate, diundecyl phthalate, alkylbenzyl phthalate (SANTICIZER
278), triphenyl phosphate (commercially available from Ferro),
KP-140, a tributoxyethyl phosphate (commercially available from
Great Lakes Chemical Corporation), MORFLEX 150, a dicyclohexyl
phthalate (commercially available from Morflex Chemical Company
Inc.), trioctyl trimellitate (commercially available from Sigma
Aldrich Co.), and the like. Plasticizers may be present in an
amount from about 0.01 percent by weight of the ink to from about
98 percent by weight of the ink, from about 0.1 percent by weight
of the ink to about 50 percent by weight of the ink, from about 5
weight percent of the ink to about 10 weight percent of the
ink.
When present, the optional additives may each, or in combination,
be present in the ink in any desired or effective amount, such as
from about 1 percent to about 10 percent by weight of the ink or
from about 3 percent to about 5 percent by weight of the ink.
In embodiments, the ink carriers for the phase change inks may have
melting points of from about 60.degree. C. to about 150.degree. C.,
for example from about 80.degree. C. to about 120.degree. C., from
about 85.degree. C. to about 110.degree. C., from about 100.degree.
C. to about 110.degree. C., or from about 105.degree. C. to about
110.degree. C. as determined by, for example, observation and
measurement on a microscope hot stage, wherein the binder material
is heated on a glass slide and observed by microscope. Higher
melting points are also acceptable, although printhead life may be
reduced at temperatures higher than 150.degree. C. Furthermore, low
energy inks have a jetting viscosity of about 9 cP to about 13 cP,
such as from about 10 cP to about 11 cP, from about 10.25 cP to
about 10.75 cP or from about 10.45 cP to about 10.85 cP, at melting
points of about 107.degree. C. to about 111.degree. C.
The ink compositions can be prepared by any desired or suitable
method. For example, each of the components of the ink carrier can
be mixed together, followed by heating, the mixture to at least its
melting point, for example from about 60.degree. C. to about
150.degree. C., 80.degree. C. to about 120.degree. C. and
85.degree. C. to about 110.degree. C. The colorant may be added
before the ink ingredients have been heated or after the ink
ingredients have been heated. When pigments are the selected
colorants, the molten mixture may be subjected to grinding in an
attritor or ball mill apparatus to effect dispersion of the pigment
in the ink carrier. The heated mixture is then stirred for about 5
seconds to about 10 minutes or more, to obtain a substantially
homogeneous, uniform melt, followed by cooling the ink to ambient
temperature (typically from about 20.degree. C. to about 25.degree.
C.). The inks are solid at ambient temperature. In a specific
embodiment, during the formation process, the inks in their molten
state are poured into molds and then allowed to cool and solidify
to form ink sticks. Suitable ink preparation techniques are
disclosed in U.S. Pat. No. 7,186,762, the disclosure of which is
incorporated herein by reference in its entirety.
The inks can be employed in apparatus for direct printing ink jet
processes and in indirect (offset) printing ink jet applications.
Another embodiment disclosed herein is directed to a process which
comprises incorporating an ink as disclosed herein into an ink jet
printing apparatus, melting the ink, and causing droplets of the
melted ink to be ejected in an imagewise pattern onto, a recording
substrate. A direct printing process is also disclosed in, for
example, U.S. Pat. No. 5,195,430, the disclosure of which is
totally incorporated herein by reference. Yet another embodiment
disclosed herein is directed to a process which comprises
incorporating an ink as disclosed herein into an ink jet printing
apparatus, melting the ink, causing droplets of the melted ink to
be ejected in an imagewise pattern onto an intermediate transfer
member, and transferring the ink in the imagewise pattern from the
intermediate transfer member to a final recording substrate. In a
specific embodiment, the intermediate transfer member is heated to
a temperature above that of the final recording sheet and below
that of the melted ink in the printing apparatus. In another
specific embodiment, both the intermediate transfer member and the
final recording sheet are heated; in this embodiment, both the
intermediate transfer member and the final recording sheet are
heated to a temperature below that of the melted ink in the
printing apparatus; in this embodiment, the relative temperatures
of the intermediate transfer member and the final recording sheet
can be (1) the intermediate transfer member is heated to a
temperature above that of the final recording substrate and below
that of the melted ink in the printing apparatus; (2) the final
recording substrate is heated to a temperature above that of the
intermediate transfer member and below that of the melted ink in
the printing apparatus; or (3) the intermediate transfer member and
the final recording sheet are heated to approximately the same
temperature. An offset or indirect printing process is also
disclosed in, for example, U.S. Pat. No. 5,389,958, the disclosure
of which is totally incorporated herein by reference. In one
specific embodiment, the printing apparatus employs a piezoelectric
printing process wherein droplets of the ink are caused to be
ejected in imagewise pattern by oscillations of piezoelectric
vibrating elements. Inks as disclosed herein can also be employed
in other hot melt printing processes, such as hot melt acoustic ink
jet printing, hot melt thermal ink jet printing, hot melt
continuous stream or deflection ink jet printing, and the like.
phase change inks as disclosed herein can also be used in printing
processes other than hot melt ink jet printing processes.
Any suitable substrate or recording sheet can be employed,
including plain papers such as XEROX 4200 papers, XEROX Image
Series papers, Courtland 4024 DP paper, ruled notebook paper, bond
paper, silica coated papers such as Sharp Company silica coated
paper, JuJo paper, HAMMERMILL LASERPRINT paper, and the like,
glossy coated papers such as XEROX Digital Color Gloss, Sappi
Warren Papers LUSTROGLOSS, specialty papers such as Xerox
DURAPAPER, and the like, transparency materials, fabrics, textile
products, plastics, polymeric films, inorganic recording mediums
such as metals and wood, and the like, transparency materials,
fabrics, textile products, plastics, polymeric films, inorganic
substrates such as metals and wood, and the like.
The inks described herein are further illustrated in the following
examples. All parts and percentages are by weight unless otherwise
indicated.
It will be appreciated that various of the above-disclosed and
other features and functions, or alternatives thereof, may be
desirably combined into many other different systems or
applications. Also, various presently unforeseen or unanticipated
alternatives, modifications, variations or improvements therein may
be subsequently made by those skilled in the art, and are also
intended to be encompassed by the following claims.
While the description above refers to particular embodiments, it
will be understood that many modifications may be made without
departing from the spirit thereof. The accompanying claims are
intended to cover such modifications as would fall within the true
scope and spirit of embodiments herein.
The presently disclosed embodiments are, therefore, to be
considered in all respects as illustrative and not restrictive, the
scope of embodiments being indicated by the appended claims rather
than the foregoing description. All changes that come within the
meaning of and range of equivalency of the claims are intended to
be embraced therein.
EXAMPLES
The examples set forth herein below and are illustrative of
different compositions and conditions that can be used in
practicing the present embodiments. All proportions are by weight
unless otherwise indicated. It will be apparent, however, that the
present embodiments can be practiced with many types of
compositions and can have many different uses in accordance with
the disclosure above and as pointed out hereinafter.
Comparative Example 1
Preparation of Phase Change Ink containing Non-modified Naphthol
Blue-Black
In a 600 mL beaker, the following were added: 26.7 g KEMAMIDE S-180
(a stearyl stearamide) commercially available from Crompton
Corporation, 18.72 g of a triamide wax (triamide as described in
U.S. Pat. No. 6,860,930), 80.69 g polywax (a polyethylene wax
having an average peak molecular weight of from about 350 to about
730 grams per mole, a polydispersity of from about 1.03 to about
3.0, and an asymmetrical molecular weight distribution skewed
toward the high molecular weight end, as described in U.S. Pat. No.
7,407,539) from Baker Petrolite, 18.72 g KE-100 resin commercially
available from Arakawa Corporation, 1.6 parts of a urethane resin
that is the adduct of three equivalents of stearyl isocyanate and a
glycerol-based alcohol (prepared as described in Example 4 of U.S.
Pat. No. 6,309,453), 0.2 parts Naugard-445 (an antioxidant)
available from Crompton Corp and 8 g SOLSPERSE 17000 commercially
available from Lubrizol Corporation.
The materials were melted in an oven at 120.degree. C., then
transferred to a Union Process 01 attritor, available from Union
Process, that was also heated to 120.degree. C., and charged with
1800 g 440 C type 1/8 inch diameter stainless steel balls available
from Hoover Precision Products. A heated impeller was attached to
the assembly. To this mixture were slowly added 4.8 g of Naphthol
Blue-Black. The impeller speed was increased such that the
impeller's peripheral velocity was about 150 centimeters per second
whereupon the attrition was continued for 18 hours. After the
removal of the steel shot by sieving, the resulted ink formed a
strong gel and could not be assessed by filtration.
Examples 1 and 2
Preparation of the Phase Change Ink of the Present Embodiments
The colorants (Naphthol Blue-Black, Nitrazine Yellow) and
N,N-dimethyldioctadecyl bromide were purchased from Sigma Aldrich.
Compounds of modified Naphthol Blue-Black and Nitrazine. Yellow
were prepared by reacting the commercially available colorant with
N,N-dimethyldioctadecyl bromide in a 1:2 ratio colorant to ammonium
bromide. The reaction proceeded very fast in water at 80.degree.
C., and the resultant insoluble compounds were isolated by
filtration using a glass frit.
Example 1
Preparation of Phase Change Ink 1 containing Modified Naphthol
Blue-Black
In a 600 mL beaker, the following were added: 26.7 g KEMAMIDE S-180
(a stearyl stearamide) commercially available from Crompton
Corporation, 18.72 g of a triamide wax (triamide as described in
U.S. Pat. No. 6,860,930), 80.69 g polywax (a polyethylene wax
having an average peak molecular weight of from about 350 to about
730 grams per mole, a polydispersity of from about 1.03 to about
3.0, and an asymmetrical molecular weight distribution skewed
toward the high molecular weight end, as described in U.S. Pat. No.
7,407,539) from Baker Petrolite, 18.72 g KE-100 resin commercially
available from Arakawa Corporation, 2.56 g of a urethane resin that
is the adduct of three equivalents of stearyl isocyanate and a
glycerol-based alcohol (prepared as described in Example 4 of U.S.
Pat. No. 6,309,453), 0.2 parts Naugard-445 (an antioxidant)
available from Crompton Corp and 8 g SOLSPERSE 17000 commercially
available from Lubrizol Corporation.
The materials were melted in an oven at 120.degree. C., then
transferred to a Union Process 01 attritor, available from Union
Process, that was also heated to 120.degree. C., and charged with
1800 g 440 C type 1/8 inch diameter stainless steel balls available
from Hoover Precision Products. A heated impeller was attached to
the assembly. To this mixture were slowly added 4.8 g of compound
modified Naphthol Blue-Black. The impeller speed was increased such
that the impeller's peripheral velocity was about 150 centimeters
per second whereupon the attrition was continued for 18 hours such
that the stainless steel balls at the top of the vessel began to
tumble gently over each other. The resultant ink was obtained after
removing the steel shot by sieving and then filtered past a 5
micron stainless steel mesh filter available from Gerard Daniel
Worldwide. The ink, as measured in frequency mode by a Rheometrics
RFS-3 rheometer, fitted with cone and plate geometry, had a complex
viscosity of 13.6 cP at 115 C.
Example 2
Preparation of Phase Change Ink 2 containing Modified Nitrazine
Yellow
In a 1000 mL beaker, the following were added: 53.4 g KEMAMIDE
S-180 (a stearyl stearamide) commercially available from Crompton
Corporation, 37.44 g of a triamide wax (triamide as described in
U.S. Pat. No. 6,860,930), 161.38 g polywax (a polyethylene wax
having an average peak molecular weight of from about 350 to about
730 grams per mole, a polydispersity of from about 1.03 to about
3.0, and an asymmetrical molecular weight distribution skewed
toward the high molecular weight end, as described in U.S. Pat. No.
7,407,539) from Baker Petrolite, 18.72 g KE-100 resin commercially
available from Arakawa Corporation, 5.12 g of a urethane resin that
is the adduct of three equivalents of stearyl isocyanate and a
glycerol-based alcohol (prepared as described in Example 4 of U.S.
Pat. No. 6,309,453), 0.2 parts Naugard-445 (an antioxidant)
available from Crompton Corp and 16 g SOLSPERSE 17000 commercially
available from Lubrizol Corporation.
The materials were melted in an oven at 120.degree. C., then
transferred to a Union Process 01 attritor, available from Union
Process, that was also heated to 120.degree. C., and charged with
1800 g 440 C type 1/8 inch diameter stainless steel balls available
from Hoover Precision Products. A heated impeller was attached to
the assembly. To this mixture were slowly added 12 g of compound
modified Nitrazine Yellow. The impeller speed was increased such
that the impeller's peripheral velocity was about 150 centimeters
per second whereupon the attrition was continued for 18 hours such
that the stainless steel balls at the top of the vessel began to
tumble gently over each other. The resultant ink was obtained after
removing the steel shot by sieving and then filtered past a 5
micron stainless steel mesh filter available from Gerard Daniel
Worldwide. The ink, as measured in frequency mode by a Rheometrics
RFS-3 rheometer, fitted with cone and plate geometry, had a complex
viscosity of 10.2 cP at 115 C.
Comparative Example 2
An ink was formed similarly to that in Example 1 except that the
colorant was a Pigment Red 176, available from Clariant
Corporation. The pigmented ink was dispersed with the aid of a
pigment synergist, SOLSPERSE 22000, available from Lubrizol
Corporation.
Comparative Example 3
An ink was formed similarly to that in Example 1 except that the
colorant was a Pigment Red 122, available from Toyo Ink. The
pigmented ink of this comparative example was dispersed with the
aid of a custom quinacridone synergist (Q-syn-1), having the
following structure:
##STR00002##
wherein n is 1-4, X is any metal, alkyl or aryl quaternary
ammonium, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are either the
same or different and each is H, CH.sub.3, OCH.sub.3 or Cl.
Comparative Example 4
An ink was formed similarly to that in Example 1 except that the
colorant was a Pigment Red 185, available from Clariant
Corporation. The pigmented ink was dispersed with the aid of a
pigment synergist, SOLSPERSE 22000, available from Lubrizol
Corporation.
Print Testing Results
Drool and Staining
As stated previously, drooling of an ink is an undesirable
phenomenon that caused when an uncontrollable and unyielding
quantity of ink continues to flow through a given print head's
nozzles after nullification of an applied pressure during a purge
cycle: Staining, also an undesirable phenomenon, is all or a
portion of the latent ink that remains on the print head even after
several purge/wipe cycles. To assess a test ink's resistance to
drooling, the ink was tested in a print head. After the test was
completed, the print head was cleaned thoroughly by flushing with
ink base.
Applied pressures that resulted in the drooling of the reference
ink base were measured and ranged from 2.1 to 2.8 inches of water,
as measured by a pressure gauge. These values were somewhat
dependent on the history of testing done on various printheads,
nevertheless, all of the reference ink bases drooled above the
minimum desired applied pressure criterion of about 1.5 inches of
water. In the examples, drool pressure was measured with a model
number DPIS8 pressure transducer available from Omega Engineering,
Inc. (Stamford, Conn.) and calibrated against a manometer. However,
other types of pressure transducers may also be used to measure
drool pressure.
The drool pressure threshold of a given test ink was determined by
first applying the pressure at the range used for the ink base. If
drooling was observed, the drooling pressure threshold of that test
ink would be determined by applying graduated decreases in
pressure. The delta drool pressure of a given test ink was also
calculated by the difference of the measured drool pressure
thresholds of the reference ink base and the test ink sample.
.DELTA.(Drool Pressure)=Drool Pressure(sample)-Drool
Pressure(reference)
Thus a test ink having a drool pressure of negative differential
inches of water, relative to a commercially available base (serving
as a control), drooled at a lower applied pressure that was
typically used in the printer. Table 1 presents the results of the
drool and staining tests.
Banding
Banding of a pigmented ink, an undesirable print feature, manifests
itself as discreet and varying optical density across the printed
page. The main reason for this occurrence is due to various levels
of pigment particles that settle in the printhead as the pigmented
ink is aged over time. Banding assessment of a test ink is employed
to provide preliminary information about print head stability of
that ink.
The banding test consists of keeping an ink in the printhead at
118.degree. C. for 72 hours in a print head. The print head
initially is flushed thoroughly with clear ink base to eliminate
all or at least the vast majority of the previous test ink to
eliminate or at least minimize the unwanted prospect of cross
contamination between inks. Upon loading the test ink in the
printer a full 100% density solid print is made on a suitable
substrate. In this case, Xerox Digital Color Xpressions Plus Copy
paper is used, and compared to the print, made from the same target
onto the same paper taken at the end of the test at which point the
test ink would have been aged in the printer for a period of time,
such as 3 days at 118.degree. C. A suitable measure of the
densometric consistency of a solid fill is optical density, and can
be determined by measuring it at discreet intervals; such as for
this series of measurements in 1 millimeter intervals. For a
measure of consistent optical density across the page (e.g., normal
to the print process direction), the percentage standard deviation
of the measured optical densities should be as low as possible. The
mean optical density of the print image is defined as the
arithmetic mean of the various individual optical densities
measured across the printed page, as calculated from:
.times..times. ##EQU00001## such that x is the average of measured
optical densities, i is an individual optical density measurement
position, x.sub.i is an individual optical density measurement
result and n is the number of optical density measurements made.
The measured optical densities' standard deviation, as an unbiased
estimator, is calculated from:
.times..times. ##EQU00002## such that s is the measured optical
densities' standard deviation, x is the average of measured optical
densities, i is an individual optical density measurement position,
x.sub.i is an individual optical density measurement result and N
is the number of optical density measurements made. The coefficient
of variation of the measured optical densities, or banding CV, is
thus calculated from: Banding CV=s/ x*100% The optical densities of
the prints were measured under ambient conditions by a
GretagMacBeth ColorEye.RTM. 7000A spectrophotometer, D50
illuminant, 2.degree. observer and ANSI Status A response. In the
absence of banding of an ink, there should also ideally be no
visually discernable differences between the two prints.
TABLE-US-00001 TABLE 1 Ink Comparative Comparative Comparative
Example Example Test Example 2 Example 3 Example 4 1 2 Novel
Colorant Preparation n/a n/a n/a Modified Modified Naphthol
Nitrazine Blue- Yellow Black .DELTA. (Drool Pressure) -1.04 -1.78
-1.60 -0.60 -0.50 (inches of water) Drool Pressure 1.16 0.33 1.20
1.56 1.61 (inches of water) Relative % Drool Pressure -47.4 -84.5
-57.1 -27.8 -23.7 Difference from Ink Base Staining (visual
observation) No Medium No No No staining Banding CV at initial
state (%) Not tested Not tested 3.4 1.7 1.7 Time ink aged in
Printer at Not tested Not tested 17 72 72 118.degree. C. (hours)
Banding CV of first print from Not tested Not tested 15.0 4.5 6.4
ink aging test (%) Visual banding differences Not tested Not tested
Very large Very Very between initial print of unaged difference
slight slight ink and first print of aged ink difference
difference
FIG. 3A and FIG. 3B demonstrate a banding test page for Ink 1 in
Example 1 at Day 0 (FIG. 3A) and after 3 days (FIG. 3B) at
118.degree. C. FIG. 3B shows the first print out after the 3 day
banding test demonstrating good stability of the non-optimized ink
as the vast majority of print head nozzles fired yielding
reasonably uniform optical density across the print. FIG. 4A and
FIG. 4B demonstrate a banding test page for Ink 2 in Example 2 at
Day 0 (FIG. 4A) and after 3 days (FIG. 4B) at 118.degree. C. FIG.
4B shows the first print out after 3 day banding test demonstrating
the good stability of the ink as all of the print head nozzles
fired yielding reasonably uniform optical density across the
print.
FIG. 5A and FIG. 5B demonstrate a banding test page for Ink 3 in
Comparative Example 4 at Day 0 (FIG. 5A) and after only 17 hours
(FIG. 5B) at 118.degree. C. FIG. 5B shows the first print out after
a 17 hour banding test demonstrating the poor stability of the ink
as several of the print head nozzles did not fire and/or fired with
a low or no amount of colorant present indicating the settling of
pigment particles had occurred during the aging of the ink in the
printhead at 118.degree. C.
Table 1 summarizes the banding results and shows the best banding
results are those that have the overall lowest variable optical
density across the printed page.
SUMMARY
In summary, the present embodiments provide for novel colorants for
use in phase change ink compositions. The novel colorants of the
present embodiments are prepared from various acid dyes derivatized
with, as an example, N,N-dimethyldioctadecyl bromide. The novel
colorants require relatively low energy input to be incorporated
into phase change ink components as inks, and are compatible with
the phase change ink components. Phase change inks comprising the
novel colorants exhibit improved drool resistance and resistance to
faceplate staining as compared to conventional pigmented inks. In
addition, the phase change inks comprising these colorants
demonstrated good stability against banding in a printer for 3 days
at 118.degree. C.
The claims, as originally presented and as they may be amended,
encompass variations, alternatives, modifications, improvements,
equivalents, and substantial equivalents of the embodiments and
teachings disclosed herein, including those that are presently
unforeseen or unappreciated, and that, for example, may arise from
applicants/patentees and others.
Unless specifically recited in a claim, steps or components of
claims should not be implied or imported from the specification or
any other claims as to any particular order, number, position,
size, shape, angle, color, or material.
All the patents and applications referred to herein are hereby
specifically, and totally incorporated herein by reference in their
entirety in the instant specification.
* * * * *